JP5898975B2 - Method for controlling content ratio of monomer unit in copolymer - Google Patents

Description

  The present invention relates to a method for controlling the content ratio of monomer units in a copolymer.

  It is known that a conjugated diene compound-nonconjugated olefin copolymer that can be effectively used as a raw material rubber for rubber products such as tires can be produced by copolymerizing an olefin and a diene under a certain catalyst. . For example, JP-T-2006-503141 (Patent Document 1) and JP-B-2-61961 (Patent Document 2) describe the copolymerization of ethylene and diene.

  By the way, in the conjugated diene compound-nonconjugated olefin copolymer, by controlling the content ratio of the monomer units (conjugated diene compound and nonconjugated olefin), the conjugated diene compound-nonconjugated olefin copolymer and Development of a method for controlling the content ratio of the conjugated diene compound and the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is required because the physical properties of the rubber composition to be included can be changed.

  In the above Patent Documents 1 and 2, etc., a method for producing a conjugated diene compound-nonconjugated olefin copolymer is disclosed, but the conjugated diene compound-nonconjugated olefin copolymer contains conjugated diene and nonconjugated olefin. A method for simply controlling the ratio has not yet been reported.

JP-T-2006-503141 Japanese Examined Patent Publication No. 2-61961

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a method for controlling the content ratio of monomer units in a copolymer, which can easily control the content ratio of a conjugated diene compound and a non-conjugated olefin in a conjugated diene compound-nonconjugated olefin copolymer. The purpose is to provide.

As a result of intensive studies to achieve the above object, the present inventors have changed the ligand in the catalyst to be used, whereby the conjugated diene compound and the nonconjugated olefin in the conjugated diene compound-nonconjugated olefin copolymer are obtained. It was found that the content ratio can be easily controlled, and the present invention has been completed.
That is, as a result of intensive studies to achieve the above object, the present inventors have changed the ligand in the catalyst to be used, thereby containing the nonconjugated olefin in the conjugated diene compound-nonconjugated olefin copolymer. The inventors have found that the ratio can be increased and have completed the present invention.
Here, the mechanism for increasing the content ratio of the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer by changing the ligand in the catalyst is as follows.
For example, by increasing the ligand, the reactivity of bulky conjugated diene (butadiene) can be reduced and the content of non-conjugated olefin (ethylene) can be increased.

〔前記一般式（１）中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ａ、Ｂ及びＣは、それぞれ独立して、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、アルデヒド残基、ケトン残基、カルボン酸残基、チオカルボン酸残基、リン化合物残基、無置換もしくは置換インデニル基、無置換もしくは置換シクロペンタジエニル基、又は、無置換もしくは置換アントラセニル基を示し、Ａ、Ｂ及びＣの少なくとも１つは、無置換もしくは置換インデニル基、無置換もしくは置換シクロペンタジエニル基、又は、無置換もしくは置換アントラセニル基である。〕
前記触媒の配位子の嵩高さの変更を、前記無置換もしくは置換インデニル基、前記無置換もしくは置換シクロペンタジエニル基、又は、前記無置換もしくは置換アントラセニル基に対して行うことを特徴とする。
目標とする共役ジエン化合物と非共役オレフィンとの含有割合に応じて、触媒の配位子を変更して前記触媒として使用すると、共役ジエン化合物−非共役オレフィン共重合体における共役ジエン化合物と非共役オレフィンとの含有割合を簡便に制御することができる。
前記触媒の配位子の変更が、前記触媒の配位子の嵩高さの変更であると、共役ジエン化合物−非共役オレフィン共重合体における共役ジエン化合物と非共役オレフィンとの含有割合をより簡便に制御することができる。
なお、共役ジエン化合物とは、分子内に二重結合を２つ有する共役化合物を示し、非共役オレフィンとは、共役ジエン化合物以外の非共役オレフィンであり、スチレンを含まないものとする。ここで、オレフィンとは、脂肪族不飽和炭化水素のことであり、炭素−炭素二重結合を１個以上有する化合物を指す。
また、「触媒の配位子」とは、触媒の中心金属に配位結合する基のことであり、例えば、後述する一般式（１）で、Ａ、Ｂ、又はＣで表される基を意味する。
さらに、「配位子の嵩高さ」とは、配位子の基本骨格に結合する置換基が多いほど（分子量が大きいほど）嵩高いとすることができる。
前記触媒の配位子の嵩高さの変更を、共役ジエン化合物と非共役オレフィンとを基準触媒を用いて重合させることにより得られた共重合体における非共役オレフィンの基準含有割合と、目標とする非共役オレフィンの目標含有割合との大小関係に基づき、前記基準触媒の配位子の少なくとも１つを、前記基準触媒の配位子の少なくとも１つと嵩高さが異なる他の配位子に変更することにより行うと、共役ジエン化合物−非共役オレフィン共重合体における共役ジエン化合物と非共役オレフィンとの含有割合をより簡便に制御することができる。
なお、「基準触媒」とは、構造式、即ち、配位子の嵩高さが既知の触媒を示すこととする。
本発明の共重合体における単量体単位の含有割合の制御方法の一例としては、前記非共役オレフィンの目標含有割合が前記基準含有割合より大のとき、前記他の配位子の嵩高さを前記基準触媒の配位子の嵩高さより大とし、前記非共役オレフィンの目標含有割合が前記基準含有割合より小のとき、前記他の配位子の嵩高さを前記基準触媒の配位子の嵩高さより小とすると、共役ジエン化合物−非共役オレフィン共重合体における共役ジエン化合物と非共役オレフィンとの含有割合をさらにより簡便に制御することができる。
前記触媒が、前記一般式（１）で表される化合物を含むと、共役ジエン化合物と非共役オレフィンとの含有割合が制御された共役ジエン化合物−非共役オレフィン共重合体を容易に製造することができる。 The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is, the method for controlling the content ratio of the monomer unit in the copolymer of the present invention is a method of polymerizing a conjugated diene compound and a non-conjugated olefin using a catalyst, and a conjugated diene compound in a copolymer obtained by polymerization. A method for controlling a content ratio of a monomer unit in a copolymer to control a content ratio with a non-conjugated olefin, wherein the catalyst has a ligand, and the target conjugated diene compound and non-conjugated olefin Depending on the content ratio, and changing the ligand of the catalyst to use as the catalyst,
In the method for controlling the content ratio of the monomer unit in the copolymer of the present invention, the change in the catalyst ligand is a change in the bulk of the catalyst ligand ,
Change the bulk of the catalyst ligand,
Based on the relationship between the reference content ratio of the nonconjugated olefin and the target content ratio of the target nonconjugated olefin in the copolymer obtained by polymerizing the conjugated diene compound and the nonconjugated olefin using the reference catalyst , By changing at least one of the ligands of the reference catalyst to another ligand that is different in bulk from at least one of the ligands of the reference catalyst,
When the target content ratio of the non-conjugated olefin is larger than the reference content ratio, the bulkiness of the other ligand is larger than the bulkiness of the ligand of the reference catalyst, and the target content ratio of the nonconjugated olefin is When smaller than the reference content ratio, the bulk of the other ligand is less than the bulk of the ligand of the reference catalyst,
The catalyst includes a compound represented by the following general formula (1),

[In the general formula (1), M represents a lanthanoid element, scandium or yttrium, and A, B, and C each independently represent a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, an aldehyde residue, A group, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue, a phosphorus compound residue, an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted anthracenyl group; , B and C are an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted anthracenyl group. ]
The bulkiness of the catalyst ligand is changed with respect to the unsubstituted or substituted indenyl group, the unsubstituted or substituted cyclopentadienyl group, or the unsubstituted or substituted anthracenyl group. .
Depending on the content ratio of the target conjugated diene compound and non-conjugated olefin, when the catalyst ligand is changed and used as the catalyst, the conjugated diene compound and non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer are used. The content ratio with the olefin can be easily controlled.
When the change of the ligand of the catalyst is a change of the bulk of the ligand of the catalyst, the content ratio of the conjugated diene compound and the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is simpler. Can be controlled.
The conjugated diene compound indicates a conjugated compound having two double bonds in the molecule, and the non-conjugated olefin is a non-conjugated olefin other than the conjugated diene compound and does not contain styrene. Here, the olefin refers to an aliphatic unsaturated hydrocarbon and refers to a compound having one or more carbon-carbon double bonds.
The “catalyst ligand” refers to a group that coordinates to the central metal of the catalyst. For example, a group represented by A, B, or C in the general formula (1) described below. means.
Furthermore, “the bulkiness of the ligand” can be made bulkier as the number of substituents bonded to the basic skeleton of the ligand increases (as the molecular weight increases).
The target is to change the bulkiness of the ligand of the catalyst, and the reference content ratio of the nonconjugated olefin in the copolymer obtained by polymerizing the conjugated diene compound and the nonconjugated olefin using the reference catalyst. Based on the magnitude relationship with the target content ratio of the non-conjugated olefin, at least one of the ligands of the reference catalyst is changed to another ligand having a bulkiness different from that of at least one of the ligands of the reference catalyst. By doing so, the content ratio of the conjugated diene compound and the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer can be more easily controlled.
The “reference catalyst” refers to a catalyst having a known structural formula, that is, a bulky ligand.
As an example of the method for controlling the content ratio of the monomer unit in the copolymer of the present invention, when the target content ratio of the non-conjugated olefin is larger than the reference content ratio, the bulkiness of the other ligand is set. When the bulk content of the ligand of the reference catalyst is larger than the bulk content of the ligand of the reference catalyst, and the target content ratio of the non-conjugated olefin is smaller than the standard content ratio of the ligand, If smaller than this, the content ratio of the conjugated diene compound and the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer can be more easily controlled.
When the catalyst contains the compound represented by the general formula (1), a conjugated diene compound-nonconjugated olefin copolymer in which the content ratio of the conjugated diene compound and the nonconjugated olefin is controlled is easily produced. Can do.

In the method for controlling the content ratio of the monomer unit in the copolymer of the present invention, it is preferable that at least one of the ligands of the catalyst is an unsubstituted or substituted indenyl group.
When at least one of the ligands of the catalyst is an unsubstituted or substituted indenyl group, a conjugated diene compound-nonconjugated olefin copolymer in which the content ratio of the conjugated diene compound and the nonconjugated olefin is controlled is more easily produced. can do.

  In the method for controlling the content ratio of the monomer unit in the copolymer of the present invention, the conjugated diene compound is preferably a conjugated diene compound having 4 to 8 carbon atoms, and a group consisting of 1,3-butadiene and isoprene. More preferably, it is at least one selected from.

In the method for controlling the content ratio of the monomer unit in the copolymer of the present invention, the non-conjugated olefin is preferably an acyclic olefin. Here, the acyclic olefin is more preferably an α-olefin having 2 to 10 carbon atoms, and the α-olefin is at least one selected from the group consisting of ethylene, propylene and 1-butene. preferable.
When the α-olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene, excellent heat resistance and ozone resistance can be obtained, and two occupies in the main chain of the copolymer. It is possible to increase the degree of freedom of design as an elastomer by reducing the ratio of heavy bonds and decreasing the crystallinity.

  ADVANTAGE OF THE INVENTION According to this invention, the control method of the content rate of the monomer unit in the copolymer which can control easily the content rate of the conjugated diene compound and nonconjugated olefin in a conjugated diene compound-nonconjugated olefin copolymer. Can be provided.

  Hereinafter, embodiments of the present invention will be specifically described with examples.

(Method for controlling the content ratio of monomer units in the copolymer)
The method for controlling the content ratio of the monomer unit in the copolymer of the present invention includes at least a polymerization step of polymerizing a conjugated diene compound and a non-conjugated olefin using a catalyst, and further, if necessary, purification (washing). It further includes a process, a drying process, and the like.
In the polymerization step, the conjugated diene compound and the non-conjugated olefin in the copolymer obtained by changing the ligand of the catalyst according to the target content ratio of the conjugated diene compound and the non-conjugated olefin. The content ratio can be controlled.
“Changing the ligand of the catalyst” is, for example, “changing the bulk of the ligand of the catalyst”, and the copolymer obtained by polymerizing a conjugated diene compound and a non-conjugated olefin using a reference catalyst. Based on the magnitude relationship between the reference content ratio of the non-conjugated olefin in the polymer and the target content ratio of the target non-conjugated olefin, at least one of the ligands of the reference catalyst is added to the ligand of the reference catalyst. It can be performed by changing to at least one other ligand having a different bulkiness.
As an example, when the target content ratio of the non-conjugated olefin is larger than the reference content ratio, the bulk of the other ligand is larger than the bulk of the ligand of the reference catalyst, When the target content ratio of the non-conjugated olefin is smaller than the reference content ratio, the bulk of the other ligand is made smaller than the bulk of the ligand of the reference catalyst.
The polymerization using the changed catalyst and the polymerization using the reference catalyst preferably have the same polymerization conditions except that the ligand of the catalyst is changed.
For example, when bis (indenyl) gadolinium bis (dimethylsilyl) amide [(C ₉ H ₇ ) ₂ GdN (SiHMe ₂ ) ₂ ] used in Example 1 described later is used as a reference catalyst, three ligands (( i) “bis (dimethylsilyl) amide”, (ii) “indenyl”, (iii) “indenyl”) with two other ligands (“indenyl”) having different bulkiness (for example, The name is changed to “2-phenylindenyl” (Example 2 described later) and “2-phenyl-1-methylindenyl” (Example 3 described later).

As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, hexane, cyclohexane, mixtures thereof etc. are mentioned.
Moreover, there is no restriction | limiting in particular as a refinement | purification (washing | cleaning) method, According to the objective, it can select suitably, Arbitrary methods can be used.
Moreover, there is no restriction | limiting in particular as a drying method, According to the objective, it can select suitably, Arbitrary methods can be used.

<Copolymer>
The copolymer is a copolymer of a conjugated diene compound and a non-conjugated olefin, and includes a non-conjugated olefin together with the conjugated diene compound as a monomer unit component in the copolymer.
By blending the conjugated diene compound-non-conjugated olefin copolymer into the rubber composition, the double bond of the conjugated diene part (part derived from the conjugated diene compound) in the copolymer is compared with the homopolymer of the conjugated diene compound. Therefore, ozone resistance is improved.

There is no restriction | limiting in particular as content of the said conjugated diene compound origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 2 mol%-less than 100 mol% are preferable.
By setting the content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer to 2 mol% or more, processability can be sufficiently secured, and by setting it to less than 100 mol%, the nonconjugated olefin can be reduced. Since a certain amount is included, an improvement in weather resistance (ozone resistance) can be expected.

There is no restriction | limiting in particular as content of the said nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, More than 0 mol% and 98 mol% or less are preferable.
The weather resistance can be improved by setting the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer to more than 0 mol%, and by making the content 98 mol% or less, the workability can be improved. It is possible to maintain and improve crack growth resistance.

Further, the amount of cis-1,4 bonds in the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected according to the purpose. % Is preferred, more than 95% is particularly preferred, and 97% or more is most preferred.
By setting the amount of cis 1,4-bond in the conjugated diene compound-derived moiety to be more than 92%, a low glass transition point (Tg) can be maintained, thereby improving physical properties such as low-temperature characteristics. Furthermore, by making the cis 1,4-bond amount of the conjugated diene compound-derived portion more than 95%, it becomes possible to improve crack growth resistance, weather resistance, and heat resistance, and by setting it to 97% or more Further, the crack growth resistance, weather resistance, and heat resistance can be further improved.
The cis-1,4 bond amount is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

  In the conjugated diene compound-nonconjugated olefin copolymer, the weight average molecular weight (Mw) is not particularly limited, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a molecular structure material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, and is 10,000 to 1,000,000. It is more preferable, and it is especially preferable that it is 50,000-600,000. If Mw exceeds 10,000,000, the moldability may be deteriorated.

  Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties may not be uniform. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and depends on the purpose. However, it is preferably 5% or less, more preferably 3% or less, and particularly preferably 2.5% or less.
When the content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is 5% or less, The weather resistance (ozone resistance) of the coalescence can be improved.
On the other hand, the content of the conjugated diene compound in the conjugated diene compound-nonconjugated olefin copolymer-derived portion derived from the conjugated diene compound has a 1,2 adduct portion (including 3,4 adduct portion) content of 3% or less, The weather resistance (ozone resistance) of a copolymer can be further improved as it is 2.5% or less.
The content of the 1,2 adduct portion (including the 3,4 adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound in the conjugated diene compound-derived portion has the same meaning as the 1,2-vinyl bond amount when the conjugated diene compound is butadiene. It is.

<< Chain structure >>
The chain structure of the copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a block copolymer, a random copolymer, a taper copolymer, and an alternating copolymer. It is done.

-Block copolymer-
The block copolymer has a structure of (AB) _x , A- (BA) _x, and B- (AB) _x (where A is a monomer unit of a non-conjugated olefin. It is a block part, B is a block part consisting of monomer units of a conjugated diene compound, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multi-block copolymer.
When the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength.

-Random copolymer-
When the conjugated diene compound-nonconjugated olefin copolymer is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, so that the copolymer does not cause phase separation, and the block portion The crystallization temperature derived from is not observed. That is, since it becomes possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer, the heat resistance is improved.

-Tapered copolymer-
The taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, a block portion composed of monomer units of a conjugated diene compound and a monomer unit of non-conjugated olefins. Consists of at least one block portion (also referred to as a block structure) of the block portion and a random portion (also referred to as a random structure) in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged. Copolymer.
The structure of the taper copolymer indicates that the composition of the conjugated diene compound component and the non-conjugated olefin component is distributed continuously or discontinuously. Here, it is preferable that the chain structure of the non-conjugated olefin component does not contain many long-chain (high molecular weight) non-conjugated olefin block components but contains many short-chain (low molecular weight) non-conjugated olefin block components.

-Alternating copolymer-
The alternating copolymer has a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain structure of -ABABABAB-, where A is a non-conjugated olefin and B is a conjugated diene compound). It is a coalescence.

By dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin, it becomes possible to control the concentration ratio of the monomers in the polymerization reaction system. It becomes possible to characterize the chain structure (that is, the arrangement of monomer units) in the resulting copolymer. Further, when the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer. The addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.
The said polymerization reaction system means the place where superposition | polymerization with a conjugated diene compound and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example.

  For example, when a block copolymer is produced, it is effective to continuously add a conjugated diene compound in the presence of a nonconjugated olefin to a polymerization reaction system in which polymerization of a nonconjugated olefin has been started in advance. In addition, what is necessary is just to repeat manufacture of a block copolymer, when manufacturing a multiblock copolymer.

  Furthermore, when producing a random copolymer, a conjugated diene compound is added one or more times in the presence of the nonconjugated olefin to the polymerization reaction system in which the polymerization of the conjugated diene compound and the nonconjugated olefin is started, Alternatively, it is effective to continuously add the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin in the presence of the non-conjugated olefin.

  Moreover, when manufacturing a taper copolymer, it becomes effective to use both the manufacturing method of a block copolymer, and the manufacturing method of a random copolymer. Specifically, (1) a non-conjugated olefin-conjugated diene compound copolymer obtained by continuously charging a conjugated diene compound in the presence of a non-conjugated olefin into a polymerization reaction system in which non-conjugated olefin polymerization has been started in advance. Or a method of continuously adding a conjugated diene compound to a polymerization reaction system containing 1 or more times and / or continuously adding a conjugated diene compound, and (2) a conjugated diene compound in the presence of a non-conjugated olefin. Examples thereof include a method in which a conjugated diene compound is continuously added, or a conjugated diene compound is continuously added, and as a result, a conjugated diene compound is continuously added to a polymerization reaction system containing a polymerized non-conjugated olefin-conjugated diene compound copolymer. Moreover, it is possible to synthesize a taper copolymer by performing polymerization using both of these methods.

  Here, with respect to the copolymer obtained by the method of the present invention, the differential scanning calorimetry (DSC) and the nuclear magnetic resonance (NMR) are used to confirm the formation of the block copolymer, the random copolymer, and the tapered copolymer. ) Is used as the main measuring means.

  The differential scanning calorimetry (DSC) is a measurement method performed in accordance with JIS K 7121-1987. Specifically, when a glass transition point derived from homopolymerization of a conjugated diene compound or a crystallization temperature derived from homopolymerization of a nonconjugated olefin can be observed by DSC, the copolymer contains a single conjugated diene compound. It shows that a block part consisting of a monomer unit or a block part consisting of a monomer unit of a non-conjugated olefin is formed. In addition, when the crystallization temperature derived from the homopolymerization of the non-conjugated olefin is not observed by DSC or a broad peak is observed compared to the peak of the crystallization temperature derived from the homopolymerization of the non-conjugated olefin, In the copolymer, a random part in which monomer units of a conjugated diene compound and a nonconjugated olefin are randomly arranged is formed.

<Conjugated diene compound>
In the conjugated diene compound-nonconjugated olefin copolymer, the conjugated diene compound used as a monomer is preferably a conjugated diene compound having 4 to 8 carbon atoms.
Specific examples of the conjugated diene compound having 4 to 8 carbon atoms include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, etc. Among these, 3-Butadiene and isoprene are preferred. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  The copolymer can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

  In addition, when controlling the injection | throwing-in of a conjugated diene compound, it is preferable to control the injection amount of a conjugated diene compound and the injection frequency of a conjugated diene compound. Examples of the method for controlling the introduction of the conjugated diene compound include a method of controlling by a program such as a computer and a method of controlling by analog using a timer or the like, but are not limited thereto. In addition, as described above, the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging. Here, when the conjugated diene compound is dividedly charged, the number of times the conjugated diene compound is charged is not particularly limited.

<Non-conjugated olefin>
In the conjugated diene compound-nonconjugated olefin copolymer, by using a nonconjugated olefin as a monomer, excellent heat resistance and ozone resistance can be obtained, and the double occupying the main chain of the copolymer. It is possible to increase the degree of design freedom as an elastomer by reducing the bonding ratio and reducing the crystallinity. Furthermore, chemical stability and self-reinforcing properties can be improved, and crack growth properties can be improved. The non-conjugated olefin is preferably an acyclic olefin, and the acyclic olefin is preferably an α-olefin having 2 to 10 carbon atoms. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with a conjugated diene can be performed efficiently.

Therefore, examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and among these, ethylene, propylene and 1-butene are preferable. Ethylene is particularly preferred. These non-conjugated olefins may be used alone or in combination of two or more.
In addition, when a block portion composed of a monomer unit of non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

  In the method of the present invention, it is preferable that the non-conjugated olefin is present in the polymerization reaction system when the conjugated diene compound is charged. In this case, it is preferable to continuously supply the non-conjugated olefin to the polymerization reaction system. Moreover, the supply method of a nonconjugated olefin is not specifically limited.

<Catalyst>
The catalyst is not particularly limited as long as it contains a compound having a modified ligand (for example, a complex), and can be appropriately selected depending on the purpose. For example, a compound having a ligand (for example, a complex) Or a polymerization catalyst composition containing a ligand-containing compound (for example, a complex) and other substances (for example, a co-catalyst). .
By changing the ligand of the compound (for example, complex) contained in the catalyst, the content ratio of the conjugated diene compound and the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer can be easily controlled. it can. For example, when the bulk of the ligand is increased, the content ratio of the non-conjugated olefin is increased.

<< Compound with Ligand >>
The compound having a ligand is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a rare earth element compound and a reaction product of the rare earth element compound and a Lewis base. Moreover, it is preferable that at least one of the ligands is an unsubstituted or substituted indenyl group.
In the polymerization reaction system, the concentration of the complex contained in the polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

-Rare earth element compound or reaction product of the rare earth element compound and Lewis base (component A)-
The rare earth element compound or the reaction product (component A) of the rare earth element compound and the Lewis base may be the rare earth element compound itself or a reaction product of the rare earth element compound and the Lewis base. Here, the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base preferably do not have a bond between the rare earth element and carbon. When the rare earth element compound and the reaction product thereof do not have a rare earth element-carbon bond, the compound is stable and easy to handle.

  Examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases, the Lewis bases may be the same or different.

前記一般式（１）中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ａ、Ｂ及びＣは、それぞれ独立して、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基、アルデヒド残基、ケトン残基、カルボン酸残基、チオカルボン酸残基、リン化合物残基、無置換もしくは置換インデニル基、無置換もしくは置換シクロペンタジエニル基、又は、無置換もしくは置換アントラセニル基を示し、Ａ、Ｂ及びＣの少なくとも１つは、無置換もしくは置換インデニル基、無置換もしくは置換シクロペンタジエニル基、又は、無置換もしくは置換アントラセニル基である。 --- Rare earth element compounds-
The rare earth element compound is not particularly limited as long as it contains a rare earth metal, and can be appropriately selected according to the purpose, but is preferably a divalent or trivalent rare earth metal salt or complex compound, The compound represented by the general formula (1) is more preferable, and at least one of A, B and C in the general formula (1) is particularly preferably an unsubstituted or substituted indenyl group.

In the general formula (1), M represents a lanthanoid element, scandium or yttrium, and A, B and C each independently represent a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, Indicates an aldehyde residue, ketone residue, carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted indenyl group, unsubstituted or substituted cyclopentadienyl group, or unsubstituted or substituted anthracenyl group , A, B and C are an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted anthracenyl group.

  The lanthanoid element is composed of elements having atomic numbers 57 to 71 in the periodic table, for example, lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium. , Lutetium. Among these, samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, and holmium Ho are preferable.

  There is no restriction | limiting in particular as said halogen atom, According to the objective, it can select suitably, For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. Among these, a chlorine atom and a bromine atom are preferable.

  The alkoxide group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Aliphatic alkoxy groups such as: phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy And aryloxide groups such as 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; and the like. Among these, 2,6-di-tert-butylphenoxy group is preferable.

  The thiolate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group Aliphatic thiolate groups such as thio tert-butoxy group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group Arylthiolate groups such as; and the like. Among these, 2,4,6-triisopropylthiophenoxy group is preferable.

  The amide group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic amide groups such as dimethylamide group, diethylamide group and diisopropylamide group; -Tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neo Arylamide groups such as pentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tri-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group, etc. Is mentioned. Among these, a bistrimethylsilylamide group is preferable.

  The silyl group is not particularly limited and may be appropriately selected depending on the intended purpose.For example, trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropyl And silyl (bistrimethylsilyl) silyl group. Among these, a tris (trimethylsilyl) silyl group is preferable.

  The aldehyde residue is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde, and the like. .

  There is no restriction | limiting in particular as said ketone residue, According to the objective, it can select suitably, For example, acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. are mentioned.

  The carboxylic acid residue is not particularly limited and may be appropriately selected depending on the intended purpose. For example, isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid , Oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade name made by Shell Chemical Co., Ltd., a synthetic acid composed of a mixture of isomers of C10 monocarboxylic acid ], Phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid, and the like.

  The thiocarboxylic acid residue is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include hexanethioic acid, 2,2-dimethylbutanethioic acid, decanothioic acid, and thiobenzoic acid.

  The phosphorus compound residue is not particularly limited and may be appropriately selected depending on the intended purpose.For example, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (phosphate 2-ethylhexyl), bis (1-methylheptyl) phosphate, dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, Phosphoric acid ester residues such as phosphoric acid (butyl) (2-ethylhexyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl); 2-ethylhexyl Monobutyl phosphonate, 2-ethylhexyl phosphonate mono-2-ethylhexyl, phenylphosphonate mono-2-ethylhexyl, 2-ethylhexylphospho Phosphonate residues such as mono-p-nonylphenyl sulfonate, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2 -Ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, 2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphine Acid, phenylphosphinic acid, p-nonylphenylphospho Residues of phosphinic acids such as fins acid; and the like.

The unsubstituted or substituted indenyl group has an indenyl ring as a basic skeleton, and may be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Suitable examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include germyl, stannyl, and silyl. The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the hydrocarbyl group described above. Examples of the metalloid group include a trimethylsilyl group. Examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） The unsubstituted or substituted cyclopentadienyl group has a cyclopentadienyl ring as a basic skeleton and is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. As carbon number of a hydrocarbyl group, 1-20 are preferable, 1-10 are more preferable, and 1-8 are especially preferable. Suitable examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include germyl, stannyl, silyl and the like, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the same as the above hydrocarbyl group. . Examples of the metalloid group include a trimethylsilyl group. Specific examples of the cyclopentadienyl ring as a basic skeleton include the following.

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す。）

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ'は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す。） Examples of the compound represented by the general formula (1) and the reaction product of the compound and Lewis base include a metallocene complex represented by the following general formula (I) and a metallocene represented by the following general formula (II). Complex, and the like. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal.

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3.)

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3.)

In the metallocene complexes represented by the general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

  The central metal M in the general formulas (I) and (II) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the catalyst can be easily synthesized. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. The alkyl group is preferably a methyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ].
X ′ contained in the silyl ligand [—SiX ′ ₃ ] is a group defined in the same manner as X in the general formula (III) described later, and preferred groups are also the same.

  The metallocene complex represented by the general formulas (I) and (II) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the metallocene complex represented by the general formula (I) and the formula (II) may exist as a monomer, or may exist as a dimer or a higher multimer.

（式中、Ｘ''はハライドを示す。） The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

(In the formula, X ″ represents a halide.)

（式中、Ｘ''はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

(In the formula, X ″ represents a halide.)

  The structure of the metallocene complex represented by the general formulas (I) and (II) is preferably determined by X-ray structural analysis.

  Furthermore, in the polymerization catalyst composition, by combining the metallocene complexes represented by the general formulas (I) and (II) with appropriate cocatalysts respectively, The molecular weight of the coalescence can be increased.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R'は、無置換もしくは置換のシクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、[Ｂ]^-は、非配位性アニオンを示す。）
中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。 The rare earth element compound other than the compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the half metallocene represented by the following general formula (III) And cation complexes.

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R ′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate. A group, an amide group, a silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents non-coordinating. Anionic anion.)
A metallocene complex having one cyclopentadienyl or a derivative thereof bonded to a central metal may be referred to as a half metallocene complex.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） In the half metallocene cation complex represented by the general formula (III), Cp ^R ′ in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that
Cp ^R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^R 'having a cyclopentadienyl ring as a basic skeleton include the following.

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^R ′ having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^R ′ having the fluorenyl ring as a basic skeleton is C
_{It can be represented by 13} H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formula (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms.
Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.

  In the general formula (III), examples of the amide group represented by X include aliphatic amide groups such as a dimethylamide group, a diethylamide group, and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group and 2,4,6-tri-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide Groups are preferred.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The half metallocene cation complex represented by the general formula (III) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the half metallocene cation complex represented by the general formula (III) may exist as a monomer, or may exist as a dimer or a higher multimer.

The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^R ′ independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the reaction is a compound selected and combined from the non-coordinating anion and cation, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of the metallocene complex represented by the general formula (I) or the formula (II) and the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structure of the half metallocene cation complex represented by the general formula (III) is preferably determined by X-ray structural analysis.

  Further, in the polymerization catalyst composition, by combining the half metallocene cation complex represented by the general formula (III) with an appropriate cocatalyst, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer are reduced. Can increase.

<< Cocatalyst >>
The promoter is not particularly limited and can be appropriately selected depending on the purpose.
Preferred are at least one selected from the group consisting of ionic compound (B-1), aluminoxane (B-2), and halogen compound (B-3), organometallic compound (C component), and the like. It is mentioned in. These promoters may be used alone or in combination of two or more. The total content of component B in the polymerization catalyst composition may be 0.1 to 50 times mol of the rare earth element compound or a reaction product (component A) of the rare earth element compound and a Lewis base. preferable.
In the ionic compound (B-1) and the halogen compound (B-3), there is no carbon atom to supply to the rare earth element compound or a reaction product (component A) of the rare earth element compound and a Lewis base. Therefore, the organometallic compound (component C) is required as a carbon supply source to the component (A). Even when the polymerization catalyst composition contains aluminoxane (B-2) as a co-catalyst, the polymerization catalyst composition can contain the organometallic compound (component C). The polymerization catalyst composition may include other components contained in a normal rare earth element compound-based polymerization catalyst composition.

-Ionic Compound (B-1)-
The ionic compound (B-1) comprises a non-coordinating anion and a cation, and reacts with a rare earth element compound (A) or a reaction product of the rare earth element compound with a Lewis base to form a cation. An ionic compound that can produce a ionic transition metal compound.

  Examples of the non-coordinating anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluoro). (Phenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride -7,8-dicarbaound decaborate.

  On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.

Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation.
Examples of the tri (substituted phenyl) carbonyl cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

  Examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (for example, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cations such as cations, N, N-diethylanilinium cations and N, N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations; Etc.

  Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

  Accordingly, the ionic compound (B-1) is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl). Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like are preferable. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them.

  In addition, as content of the ionic compound (B-1) in the said polymerization catalyst composition, 0.1-10 times mole is preferable with respect to (A) component, and it is still more preferable that it is about 1 time mole.

-Aluminoxane (B-2)-
Aluminoxane (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, a chain aluminoxane or a cyclic aluminoxane having a repeating unit represented by the general formula: (—Al (R ′) O—) (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, The hydrocarbon group may be substituted with a halogen atom and / or an alkoxy group, and the polymerization degree of the repeating unit is preferably 5 or more, more preferably 10 or more.
Here, examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among these, a methyl group is preferable.
Examples of the organoaluminum compound used as the raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used.
The aluminoxane is preferably an alkylaminoxan such as methylaluminoxane (MAO) or modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem) and the like are preferable.
The aluminoxane content in the polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to do so.

-Halogen compound (B-3)-
The halogen compound (B-3) includes at least one of (i) a Lewis acid, (ii) a complex compound of a metal halide and a Lewis base, and (iii) an organic compound containing an active halogen. By reacting with the rare earth element compound as the component (A) or a reaction product of the rare earth element compound with a Lewis base, a halogenated transition metal compound or a compound with insufficient charge at the transition metal center can be produced. In addition, it is preferable that content of the sum total of the halogen compound in the said polymerization catalyst composition is 1-5 times mole with respect to (A) component.

-(I) Lewis acid--
As the Lewis acid, a boron-containing halogen compound such as B (C ₆ F ₅ ) _{3 and} an aluminum-containing halogen compound such as Al (C ₆ F ₅ ) ₃ can be used, and the III, IV, V in the periodic table can be used. Halogen compounds containing an element belonging to Group VI, VIII can also be used. The Lewis acid is preferably an aluminum halide or an organometallic halide. Moreover, as a halogen element, chlorine or bromine is preferable.
Examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride. , Dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride, five Li chloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, and the like.
Among these, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are preferable.

-(Ii) Complex compound of metal halide and Lewis base--
---- Metal halide ---
Examples of the metal halide constituting the complex compound of a metal halide and a Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, Calcium iodide, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride , Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Is mentioned.
Among these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferable, and magnesium chloride, manganese chloride, zinc chloride, and copper chloride are more preferable.

--- Lewis base ---
Examples of the Lewis base constituting the complex compound of a metal halide and a Lewis base include phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols, and the like.
Specific examples of the Lewis base include, for example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphino. Ethane, acetylacetone, benzoylacetone, propionitrileacetone, valerylacetone, ethylacetylacetone, methylacetoacetate, ethylacetoacetate, phenylacetoacetate, dimethylmalonate, diethylmalonate, diphenylmalonate, acetic acid, octanoic acid, 2- Ethyl-hexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl- Hexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, and the like.
Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

-(Iii) Organic compound containing active halogen--
Examples of the organic compound containing active halogen include benzyl chloride.

-Organometallic compound (component C)-
The organometallic compound (component C) has the following general formula (i):
YR ¹ _a R ² _b R ³ _c (i)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different, and Y is a periodic table. When the metal is selected from Group 1, a is 1, and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a And b is 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. The following general formula (X):
AlR ¹¹ R ¹² R ¹³ ... (X)
[Wherein, R ¹¹ and R ¹² are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ¹³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and is preferably an organoaluminum compound.

--Organic aluminum compound of general formula (X)-
Examples of the organoaluminum compound of the general formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, Trialkylaluminum such as tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, hydrogen Dihexyl aluminum hydride, diisohexyl aluminum hydride, dioctyl aluminum hydride, diisooctyl aluminum hydride, etc. Mini um hydride, ethyl aluminum dihydride, n- propyl aluminum dihydride, isobutyl aluminum dihydride; and the like; dialkyl aluminum chloride, alkyl aluminum dichloride. These organometallic compounds can be used singly or as a mixture of two or more.
Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable.
In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is more preferable that it is about 10 times mole.

  In the method of the present invention, the polymerization of the conjugated diene compound and the non-conjugated olefin may be performed in the presence of the following other polymerization catalyst or other polymerization catalyst composition.

［式中、Ｍ²¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して、無置換もしくは置換インデニル、無置換もしくは置換シクロペンタジエニル、又は、無置換もしくは置換アントラセニルを示し、Ｒ²¹及びＲ²²は、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ²¹及びＲ²²は、Ｍ²¹及びＡｌにμ配位しており、Ｒ²³及びＲ²⁴は、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す］で表されるメタロセン系複合触媒が更に好ましい。なお、メタロセン系複合触媒とは、ランタノイド元素、スカンジウム又はイットリウムの希土類元素と周期律表第１３族元素とを有する化合物である。また、これらのメタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、共重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、共重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、該メタロセン系複合触媒であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 <Other polymerization catalyst, other polymerization catalyst composition>
-Other polymerization catalysts-
As other polymerization catalyst, the following formula (A):
R _a MX _b QY _b (A)
[Wherein R independently represents unsubstituted or substituted indenyl, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted anthracenyl, wherein R is coordinated to M, and M is a lanthanoid Element represents scandium or yttrium, X represents independently a hydrocarbon group having 1 to 20 carbon atoms, X is μ-coordinated to M and Q, and Q represents a group 13 element in the periodic table. And Y represents a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, Y is coordinated to Q, and a and b are 2.] Are preferably mentioned, and the following general formula (XX):

[ ^Wherein M ²¹ represents a lanthanoid element, scandium or yttrium, and Cp ^R each independently represents an unsubstituted or substituted indenyl, an unsubstituted or substituted cyclopentadienyl, or an unsubstituted or substituted anthracenyl. , R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 20 carbon atoms, R ²¹ and R ²² are μ-coordinated to M ²¹ and Al, and R ²³ and R ²⁴ are And each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom], and further preferred is a metallocene composite catalyst. The metallocene-based composite catalyst is a compound having a lanthanoid element, a scandium or yttrium rare earth element and a Group 13 element in the periodic table. Moreover, by using these metallocene composite catalysts, for example, a catalyst that is previously combined with an aluminum catalyst, the amount of alkylaluminum used during the synthesis of the copolymer can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the formula (A), each R is independently an unsubstituted or substituted indenyl, an unsubstituted or substituted cyclopentadienyl, or an unsubstituted or substituted anthracenyl, and the R is coordinated to the metal M. ing.
Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. Can be mentioned.
Specific examples of substituted cyclopentadienyl include, for example, pentamethylcyclopentadienyl.

  In the formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, and thallium.

  In the formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and the like.

On the other hand, in the metallocene composite catalyst represented by the formula (XX), the metal M ²¹ in the formula (XX) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the formula (XX), Cp ^R is unsubstituted or substituted indenyl, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted anthracenyl.
The unsubstituted or substituted indenyl, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted anthracenyl in the formula (XX) is the same as the unsubstituted or substituted indenyl group, unsubstituted or substituted cyclopenta in the general formula (1). It is the same as a dienyl group or an unsubstituted or substituted anthracenyl group. Note that the two Cp ^R 's in formula (XX) may be the same or different from each other.

In the formula (XX), R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and the R ²¹ and R ²² are μ-coordinated to M ²¹ and Al. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the formula (XX), R ²³ and R ²⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

The metallocene composite catalyst can be obtained, for example, by reacting the metallocene complex represented by the formula (I) with an organoaluminum compound represented by AlR ²⁵ R ²⁶ R ²⁷ in a solvent. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by X-ray structural analysis.

The organoaluminum compound is represented by AlR ²⁵ R ²⁶ R ²⁷ , wherein R ²⁵ and R ²⁶ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and R ²⁷ is A monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ²⁷ may be the same as or different from R ²⁵ or R ²⁶ . Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and the like. Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum. , Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl al Bromide dihydride, isobutyl aluminum dihydride, and the like. Among them, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 2 to 50 times mol, more preferably about 3 to 5 times mol for the metallocene complex.

-Other polymerization catalyst composition-
Furthermore, as the other polymerization catalyst composition, a polymerization catalyst composition containing the metallocene composite catalyst and a boron anion can also be preferably mentioned. The polymerization catalyst composition further contains a normal metallocene complex. Other components contained in the polymerization catalyst composition, such as a promoter, may be included. The metallocene composite catalyst and the boron anion are also referred to as a two-component catalyst. According to the polymerization catalyst composition, a conjugated diene compound-nonconjugated olefin copolymer can be produced in the same manner as the metallocene composite catalyst.

  Specific examples of the boron anion constituting the two-component catalyst in the polymerization catalyst composition include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundeborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  The boron anion can be used as an ionic compound combined with a cation. Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. As the tri (substituted phenyl) carbonyl cation, specifically, a tri (methyl) Phenyl) carbonium cation, and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation; and the like. Examples of the phosphonium cation include a triarylphosphonium cation such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like are preferable. The ionic compound composed of a boron anion and a cation is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene composite catalyst.

Preferred examples of the cocatalyst that can be used in the polymerization catalyst composition include an aluminoxane in addition to the organoaluminum compound represented by the above-described AlR ²⁵ R ²⁶ R ²⁷ . The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.

  In the method of the present invention, when the polymerization catalyst or the polymerization catalyst composition is used, for example, it can be carried out in the same manner as in the method for producing a polymer by a polymerization reaction using a conventional coordination ion polymerization catalyst. Here, when the method of the present invention uses the polymerization catalyst composition, for example, (1) a component of the polymerization catalyst composition is added to a polymerization reaction system containing a conjugated diene compound and a non-conjugated olefin as monomers. The polymerization catalyst composition may be prepared separately and prepared in the reaction system, or (2) a previously prepared polymerization catalyst composition may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001 times mole-0.01 times mole with respect to the sum total of a conjugated diene compound and a nonconjugated olefin.

  In the method of the present invention, the polymerization may be stopped using a polymerization terminator such as ethanol or isopropanol.

  The polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. The pressure for the polymerization reaction is preferably in the range of 0.1 MPa to 10 MPa in order to sufficiently incorporate the conjugated diene compound and the non-conjugated olefin into the polymerization reaction system. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example. it can.

In the method of the present invention, when polymerizing a conjugated diene compound and a non-conjugated olefin, the concentration (mol / l) of the conjugated diene compound and the concentration (mol / l) of the non-conjugated olefin at the start of the polymerization are as follows:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Example 1)
After adding 200 mL of a toluene solution containing 30.2 g (0.56 mol) of 1,3-butadiene to a sufficiently dried 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box in a nitrogen atmosphere, a bis (indenyl) gadolinium bis (dimethylsilyl) amide [(C ₉ H ₇ ) ₂ GdN (SiHMe ₂ ) ₂ represented by the following structural formula (1) is placed in a glass container. ] (Reaction product of the rare earth element compound or the rare earth element compound and Lewis base (component A)) 7.5 μmol, dimethylanilinium tetrakis (pentafluorophenyl) borate (Me ₂ NHPhB (C ₆ F ₅ ) ₄ ) ( 7.5 μmol of the ionic compound (B-1)) and 0.90 mmol of diisobutylaluminum hydride (the organometallic compound (component C): diisobutylaluminum hydride) were charged and dissolved in 10 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 7.0 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 90 minutes. After polymerization, 2, 2 '? Methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 1% mL of 5% by weight isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol, followed by vacuum drying at 70 ° C. Copolymer A was obtained. The yield of the obtained copolymer A was 30.5 g.

(Example 2)
In Example 1, instead of bis (indenyl) gadolinium bis (dimethylsilyl) amide, bis (2-phenylindenyl) gadolinium bis (dimethylsilyl) amide represented by the following structural formula (2) [(2-PhC ₉ Polymerization was carried out in the same manner except that H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was used, whereby Copolymer B was obtained. The yield of the obtained copolymer B was 32.5 g.

但し、構造式（３）において、Ｍｅは、メチル基を表す。 (Example 3)
In Example 1, instead of bis (indenyl) gadolinium bis (dimethylsilyl) amide, bis (2-phenyl-1-methylindenyl) gadolinium bis (dimethylsilyl) amide represented by the following structural formula (3) [( Copolymer C was obtained by performing polymerization in the same manner except that 2-Ph-1-MeC ₉ H ₅ ) ₂ GdN (SiHMe ₂ ) ₂ ] was used. The yield of the obtained copolymer C was 34.2 g.

However, in Structural Formula (3), Me represents a methyl group.

The catalysts of Examples 1 to 3 are common in that the central metal is gadolinium, one of the ligands is bis (dimethylsilyl) amide, and the two basic skeletons of the remaining ligands are indenyl, Only the substituent bonded to indenyl is changed. By comparing these Examples 1 to 3, the influence of the bulkiness of the ligand on the ethylene content can be understood.
Example 4
In Example 1, instead of bis (indenyl) gadolinium bis (dimethylsilyl) amide, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(C ₅ Me ₅ ) ₂ Gd (μ-Me) ) Polymerization was carried out in the same manner except that ₂ AlMe ₂ ] was used, and copolymer D was obtained. The yield of the obtained copolymer D was 31.5 g.

  For the ethylene-butadiene copolymers A to D prepared as described above, the weight average molecular weight (Mn), the molecular weight distribution (Mw / Mn), the cis-1,4 bond amount, and the ethylene content (mol%) are as follows. Measurement and evaluation were carried out by the following methods. The results are shown in Tables 1-2.

(1) Weight average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMHHR-H (S) HT × 2, detector: differential refractometer (RI)] on the basis of monodisperse polystyrene, The weight average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the ethylene-butadiene copolymers A to D were determined. The measurement temperature is 140 ° C.
(2) Microstructure (cis-1,4 bond amount)
The microstructure (cis-1,4 bond amount) of the butadiene moiety in the ethylene-butadiene copolymers A to D was determined as cis-1 by ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). , 4 bond components (26.5-27.5 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). The calculated values of cis-1,4 bond amount (%) are shown in Tables 1-2.
(3) Content of ethylene-derived part (mol%)
The content (mol%) of the ethylene-derived portion in the ethylene-butadiene copolymers A to D was determined by 13C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm) as a whole of the ethylene-bonded component (28.5). −30.0 ppm) and the total ratio of the butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). Tables 1 and 2 show the ethylene content (mol%). In addition, the value which subtracted the content rate (mol%) of the obtained ethylene origin part from 100 mol% becomes the content rate (mol%) of a butadiene origin part (conjugated diene compound origin part).

  In the copolymers A to C in Table 1, the ethylene content (mol%) increases as the ligand becomes bulky in the order of A, B, and C, and the catalyst ligand is changed. It was found that the content ratio of butadiene and ethylene in the ethylene-butadiene copolymer can be controlled.

  The conjugated diene compound-nonconjugated olefin copolymer in which the content ratio of the monomer units is controlled by the method of the present invention can be used, for example, for all elastomer products, particularly for tire members.

Claims (6)

Control of the content ratio of conjugated diene compound and nonconjugated olefin in the copolymer obtained by polymerizing conjugated diene compound and nonconjugated olefin using a catalyst A rate control method,
The catalyst has a ligand;
Depending on the content ratio of the target conjugated diene compound and non-conjugated olefin, the ligand of the catalyst is changed and used as the catalyst,
The change of the catalyst ligand is a change in the bulk of the catalyst ligand ,
Change the bulk of the catalyst ligand,
Based on the relationship between the reference content ratio of the nonconjugated olefin and the target content ratio of the target nonconjugated olefin in the copolymer obtained by polymerizing the conjugated diene compound and the nonconjugated olefin using the reference catalyst , By changing at least one of the ligands of the reference catalyst to another ligand that is different in bulk from at least one of the ligands of the reference catalyst,
When the target content ratio of the non-conjugated olefin is larger than the reference content ratio, the bulkiness of the other ligand is larger than the bulkiness of the ligand of the reference catalyst, and the target content ratio of the nonconjugated olefin is When smaller than the reference content ratio, the bulk of the other ligand is less than the bulk of the ligand of the reference catalyst,
The catalyst includes a compound represented by the following general formula (1),

[In the general formula (1), M represents a lanthanoid element, scandium or yttrium, and A, B, and C each independently represent a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, an aldehyde residue, A group, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue, a phosphorus compound residue, an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted anthracenyl group; , B and C are an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted anthracenyl group. ]
The bulkiness of the catalyst ligand is changed with respect to the unsubstituted or substituted indenyl group, the unsubstituted or substituted cyclopentadienyl group, or the unsubstituted or substituted anthracenyl group. The method for controlling the content ratio of the monomer units in the copolymer.   The method for controlling the content ratio of monomer units in the copolymer according to claim 1, wherein the conjugated diene compound is a conjugated diene compound having 4 to 8 carbon atoms. The method for controlling the content ratio of a monomer unit in a copolymer according to claim 2 , wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The method for controlling the content ratio of monomer units in the copolymer according to claim 1, wherein the non-conjugated olefin is an acyclic olefin. The said acyclic olefin is a C2-C10 alpha olefin, The control method of the content rate of the monomer unit in the copolymer of Claim 4 characterized by the above-mentioned. The method for controlling the content ratio of monomer units in a copolymer according to claim 5 , wherein the α-olefin is at least one selected from the group consisting of ethylene, propylene and 1-butene.